CN105111233A - Preparation method of octaphenyl silsesquioxane - Google Patents
Preparation method of octaphenyl silsesquioxane Download PDFInfo
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Abstract
The invention discloses a preparation method of octaphenyl silsesquioxane. The preparation method comprises the steps of firstly, placing a reactor into an ice-water bath, adding a mixed solution of an organic solvent and deionized water into the reactor, and then, adding phenylsilane; then, starting to stir to carry out hydrolysis reaction for 20-60 minutes, then, standing, washing an organic phase, and drying to obtain a precursor hydrolysis product; adding the precursor hydrolysis product into an original reaction vessel, then, adding a mixture of a catalyst and a solvent into the original reaction vessel, and carrying out backflow reaction at the temperature of 20-250 DEG C for 5-100 hours to separate out a great number of white sediments; and then, purifying in a way of filtering, washing or dissolving and re-crystallizing the sediments, and drying to obtain octaphenyl silsesquioxane. According to the preparation method, octaphenyl-functionalized POSS with relatively high molecular weight and relatively high yield is controllably prepared by taking phenylsilane as a raw material through a low-temperature feeding and two-step hydrolysis process; in addition, the preparation process is simple, the yield is relatively high, and the preparation period is short.
Description
Technical field
The invention belongs to organic polymer material field, be specifically related to a kind of preparation method of octaphenyl cagelike silsesquioxane.
Technical background
Hybrid material is the compound of two kinds of different kind of material, and past people utilize large-sized hydridization once to obtain the comparatively excellent material of some performance, and it easily processes the feature with inorganic materials high strength with organic polymer.But the hydridization only rested in big scale to meet the hi-tech requirement of current information epoch to material.For this reason, the hydridization of small scale hydridization and nanoscale and molecular level is suggested, to obtaining multi-functional, superintegrated matrix material.
The general molecular formula of cage modle polysilsesquioxane (POSS) is expressed as (RSiO
3/2) n(n>=4), the skeleton that it is formed by Si-O-Si and the nanoparticle that the side chain that organic group is formed forms.It has the core of similar inorganic silicon dioxide and organic side chain, is hybridized nanometer compound unique at present.POSS, as a kind of nano modifier, has been widely used for the organic-inorganic nanocomposite that processability is excellent.
POSS is used alone and has little significance, have to pass through functionalization and modification could and body material form the object of inorganic/organic Hybrid Materials.An important directions of current POSS chemical field research is exactly functionalized, and so-called functionalized referring to introduces functional group on existing POSS molecule.Functionalized method mainly contains two large classes: one, " drift angle-attach the names of pre-determined candidates " method; Two, functional group conversions's method.Through the POSS of functionalization and modification, because of the difference of organo-functional group type and number on its eight angles, it can be respectively applied for grafting, copolymerization, crosslinking reaction, thus obtains linear, grafting that silica skeleton is core or three-dimensional cross-linked organic/inorganic nano hydridization polymer composite.Owing to introducing a small amount of POSS, the performance of polymer materials just can show significant raising, and as flame retardant properties, mechanical property, processing characteristics, permeability energy etc. are all significantly improved, POSS will bring revolutionary change to conventional polymeric materials.Therefore explore POSS synthesis and functionalization and modification variation route, to reduce costs, thus applying for large-scale industrialization and lay the foundation.
Along with going deep into of the research to POSS and derivative thereof, it is found that compared with simple function group or bifunctional POSS, polyfunctional group POSS has more reactive behavior point, it can with polymer chain or segment with more covalent bonds, make the combination of itself and organic polymer more firm, disperse more even.And, carried out the cross-linking density of telomerized polymer by the number changing functional group in POSS molecule, significantly can change the physical properties of multipolymer.
It is one important in polyfunctional group POSS that octaphenyl replaces cagelike silsesquioxane, and it can react with each family macromolecule functional group and generate multipolymer, also can by the substitution reaction synthesis polyfunctional group POSS of phenyl ring.The diversity of phenyl functionalization and the advantage such as the rigidity of aromatic structure and thermotolerance, make the study on the modification of phenyl POSS in recent years receive increasing concern.To be nineteen sixty utilize phenyl-trichloro-silicane to obtain through a complicated multistep condensation reaction after potassium hydroxide is hydrolyzed by Brown etc. to octaphenyl POSS, and its preparation method is more complicated, and productive rate is lower, is not suitable for suitability for industrialized production.
Summary of the invention
The object of the invention is the preparation method providing a kind of octaphenyl cagelike silsesquioxane, has simple to operate, that productive rate is higher feature.
A preparation method for octaphenyl cagelike silsesquioxane, is characterized in that comprising the following steps:
(1) first reactor is placed in ice-water bath, the mixing solutions of organic solvent and deionized water is added in reactor, then adds phenyl silane; Then open stirring to be hydrolyzed after reaction 20 ~ 60min and to leave standstill; Finally separate with the water layer of separating funnel by reactor lower floor, then its organic phase is washed and dried, obtain forerunner's hydrolysate;
(2) forerunner's hydrolysate is added in former reaction vessel, then add the mixture of catalysts and solvents wherein, at 20 ~ 250 DEG C of temperature after back flow reaction 5 ~ 100h, namely have a large amount of white depositions to separate out; Then throw out filtered, wash or purify by the mode of dissolve-repreparation, dry to obtain product.
Further scheme, is filled with protection of inert gas in the reactor in described step (1), and with agitator and prolong; Described agitator is mechanical stirrer or magnetic stirring apparatus.
Organic solvent in described step (1) is benzene, toluene, tetrahydrofuran (THF) or Virahol.
Phenyl silane in described step (1) is phenyl-trichloro-silicane, phenyltrimethoxysila,e or phenyl triethoxysilane.
The concentration of the phenyl silane in described organic phase is 0.1 ~ 0.5g/mL.
Deionized water in described step (1) and the volume ratio of organic solvent are 1 ~ 2:1.
The washings washed organic phase in described step (1) is saturated nacl aqueous solution, methyl alcohol, deionized water or acetonitrile, and carrying out dry siccative to organic phase is anhydrous sodium sulphate.
Catalyzer in described step (2) is potassium hydroxide, sodium hydroxide, tetraethyl ammonium hydroxide or lithium hydroxide; The volumetric molar concentration that described catalyzer accounts for the mixture of catalysts and solvents is 0.5 ~ 2mol/L.
Solvent in described step (2) is one or more in benzene,toluene,xylene, acetone, ethanol, and the volume ratio of solvent and organic phase is 1 ~ 3:1.
Washing in described step (2) is washed with ether, methylene dichloride or acetone; Bake out temperature is 60 ~ 80 DEG C; The solvent of described dissolve-repreparation is methylene dichloride and acetone.
The present invention take phenyl silane as raw material, adopt low temperature feeding mode and two-step hydrolysis technique, by the concentration in the mixed solvent of allotment catalyzer and hydrolysate and temperature of reaction etc., controllably prepare the comparatively large and functionalized POSS of octaphenyl that productive rate is higher of molecular weight, as shown in formula 1 below, preparing molecular weight with phenyl-trichloro-silicane is 3.4 × 10
5octaphenyl cagelike silsesquioxane; As shown in Equation 2, preparing molecular weight with phenyl triethoxysilane is 1.5 × 10
5octaphenyl cagelike silsesquioxane.
(formula 1)
(formula 2)
So the present invention take phenyl silane as raw material, adopt low temperature feeding mode and two-step hydrolysis technique, by the concentration in the mixed solvent of allotment catalyzer and hydrolysate, controllably prepare the comparatively large and functionalized POSS of octaphenyl that productive rate is higher of molecular weight.Compared with the method preparing the functionalized POSS of octaphenyl with tradition, preparation technology of the present invention is simple, productive rate is higher, and preparation cycle is short, has market using value.
Embodiment
Specific embodiments is shown in following example.But the invention is not restricted to following examples, the present invention explains in widely.
example one:
(1) the 500mL there-necked flask that prolong and agitator are housed is placed in ice-water bath, is filled with rare gas element protection to its inside, then add 100mL benzene and 150mL deionized water, then add 28g phenyl triethoxysilane; Turn on agitator leaves standstill after being hydrolyzed and reacting 40min; Finally to filter out in there-necked flask the water layer of bottom with separating funnel, by anhydrous sodium sulphate, dry forerunner's hydrolysate is carried out to it again to after organic phase deionized water wash three times;
(2) configure the potassium hydroxide-ethanol solution 100mL of 0.5mol/L, drop into again together with forerunner's hydrolysate in the there-necked flask in (1) and mix.In 110 DEG C of back flow reaction 72h, filter to obtain white mass, by washed with dichloromethane more than 3 times, then put into vacuum drying oven 60 DEG C of dry 24h, obtaining molecular weight is 1.5 × 10
5, productive rate be about 81%(according to phenyl silane charging capacity calculate) octaphenyl cagelike silsesquioxane.
example two:
(1) the 500ml there-necked flask that prolong and agitator are housed is placed in ice-water bath, is filled with rare gas element protection to its inside, then add 100ml toluene and 200mL deionized water mixed solution, then add 28g phenyltrimethoxysila,e; Unlatching stirring leaves standstill after being hydrolyzed and reacting 20min; Finally to filter out in there-necked flask the water layer of bottom with separating funnel, and three times are washed to wherein organic phase saturated nacl aqueous solution, then by anhydrous sodium sulphate, dry forerunner's hydrolysate is carried out to it;
(2) configure the sodium hydroxide acetone soln 150mL of 2mol/L, drop into again together with forerunner's hydrolysate in the there-necked flask in (1) and mix.In 250 DEG C of back flow reaction 5h, filtering to obtain white mass, is 6.8 × 10 with in washed with diethylether 3 final vacuum loft drier, 70 DEG C of dry 24h obtain molecular weight
4, productive rate be about 64.8%(according to phenyl silane charging capacity calculate) octaphenyl cagelike silsesquioxane.
example three:
(1) the 500ml there-necked flask that prolong and agitator are housed is placed in ice-water bath, is filled with rare gas element protection to its inside, then add 30ml tetrahydrofuran (THF) and 30mL deionized water, then 15g phenyl-trichloro-silicane is slowly added dropwise to wherein.Turn on agitator is hydrolyzed after reaction 60min and leaves standstill, and finally to filter out in there-necked flask the water layer of bottom with separating funnel, carries out dry forerunner's hydrolysate again to after organic phase methanol wash three times by anhydrous sodium sulphate to it;
(2) according to the proportioning configuration solution 30mL of acetone/ethanol=4:1, then the mixture that tetraethyl-sodium hydroxide is configured to 1mol/L is added; It is risen in the there-necked flask dropped into again in (1) with forerunner's hydrolysate and mixes.In 20 DEG C of back flow reaction 100h, obtain white product.After being leached by product, after washing with acetone, then carry out recrystallization purification with methylene dichloride and acetone, finally put into 80 DEG C of baking ovens again and dry, obtain molecular weight about 3.4 × 10
5productive rate be about 70%(according to phenyl silane charging capacity calculate) octaphenyl cagelike silsesquioxane.
Above embodiment is not limited only to protection scope of the present invention, all modify based on basic thought of the present invention or change all belong to protection scope of the present invention.
Claims (10)
1. a preparation method for octaphenyl cagelike silsesquioxane, is characterized in that comprising the following steps:
(1) first reactor is placed in ice-water bath, the mixing solutions of organic solvent and deionized water is added in reactor, then adds phenyl silane; Then open stirring to be hydrolyzed after reaction 20 ~ 60min and to leave standstill; Finally separate with the water layer of separating funnel by reactor lower floor, then its organic phase is washed and drying, obtain forerunner's hydrolysate;
(2) forerunner's hydrolysate is added in former reaction vessel, then add the mixture of catalysts and solvents wherein, at 20 ~ 250 DEG C of temperature after back flow reaction 5 ~ 100h, namely have a large amount of white depositions to separate out; Then throw out filtered, wash or purify by the mode of dissolve-repreparation, dry to obtain product.
2. preparation method according to claim 1, is characterized in that: be filled with protection of inert gas in the reactor in described step (1), and with agitator and prolong; Described agitator is mechanical stirrer or magnetic stirring apparatus.
3. preparation method according to claim 1, is characterized in that: the organic solvent in described step (1) is benzene, toluene, tetrahydrofuran (THF) or Virahol.
4. preparation method according to claim 1, is characterized in that: the phenyl silane in described step (1) is phenyl-trichloro-silicane, phenyltrimethoxysila,e or phenyl triethoxysilane.
5. preparation method according to claim 1, is characterized in that: the concentration of the phenyl silane in described organic phase is 0.1 ~ 0.5g/mL.
6. preparation method according to claim 1, is characterized in that: the deionized water in described step (1) and the volume ratio of organic solvent are 1 ~ 2:1.
7. preparation method according to claim 1, it is characterized in that: the washings washed organic phase in described step (1) is saturated nacl aqueous solution, methyl alcohol, deionized water or acetonitrile, carrying out dry siccative to organic phase is anhydrous sodium sulphate.
8. preparation method according to claim 1, is characterized in that: the catalyzer in described step (2) is potassium hydroxide, sodium hydroxide, tetraethyl ammonium hydroxide or lithium hydroxide; The volumetric molar concentration that described catalyzer accounts for the mixture of catalysts and solvents is 0.5 ~ 2mol/L.
9. preparation method according to claim 1, is characterized in that: the solvent in described step (2) is one or more in benzene,toluene,xylene, acetone, ethanol, and the volume ratio of solvent and organic phase is 1 ~ 3:1.
10. preparation method according to claim 1, is characterized in that: the washing in described step (2) is washed with ether, methylene dichloride or acetone; Bake out temperature is 60 ~ 80 DEG C; The solvent of described dissolve-repreparation is methylene dichloride and acetone.
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Cited By (4)
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| CN105905913A (en) * | 2016-04-19 | 2016-08-31 | 广州赫尔普化工有限公司 | Preparation of silicon dioxide microsphere with nonionic/anionic-combined-type surfactant as soft template |
| CN107474253A (en) * | 2017-08-24 | 2017-12-15 | 重庆三圣实业股份有限公司 | A kind of modified concrete early strength agent and preparation method thereof |
| CN107585802A (en) * | 2017-10-13 | 2018-01-16 | 南京旭羽睿材料科技有限公司 | A kind of graphene composite material applied to Industrial Waste Water Treatments |
| CN113234225A (en) * | 2021-06-10 | 2021-08-10 | 山东硅科新材料有限公司 | Method for simply and efficiently preparing T8-POSS |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105905913A (en) * | 2016-04-19 | 2016-08-31 | 广州赫尔普化工有限公司 | Preparation of silicon dioxide microsphere with nonionic/anionic-combined-type surfactant as soft template |
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| CN107474253A (en) * | 2017-08-24 | 2017-12-15 | 重庆三圣实业股份有限公司 | A kind of modified concrete early strength agent and preparation method thereof |
| CN107585802A (en) * | 2017-10-13 | 2018-01-16 | 南京旭羽睿材料科技有限公司 | A kind of graphene composite material applied to Industrial Waste Water Treatments |
| CN113234225A (en) * | 2021-06-10 | 2021-08-10 | 山东硅科新材料有限公司 | Method for simply and efficiently preparing T8-POSS |
| CN113234225B (en) * | 2021-06-10 | 2022-08-02 | 山东硅科新材料有限公司 | Method for simply and efficiently preparing T8-POSS |
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